Cyclohexenone derivatives, preparation and use thereof as herbicides

ABSTRACT

Cyclohexenone derivative of the formula ##STR1## where A is oxygen or NOR 8 , where R 8  is alkyl, alkenyl, alkynyl, haloalkyl or haloalkenyl, chlorothienyl or alkoxyalkyl 
     B is O, S, SO or SO 2 , 
     X is hydrogen or methoxycarbonyl, 
     R 1  is hydrogen, carbonylalkyl, benzoyl or a cation, 
     R 2  is alkyl, 
     R 3  and R 4  are hydroxyl, chlorine, bromine, thioalkylcarboxyl, thiocarbonylalkyl, alkylcarbonyloxy, alkoxy, or alkylthio, or R 3  and R 4  together epoxy, 
     R 5  and R 6  are hydrogen or methyl or R 5  and R 6  are together methyleneoxyethylene, and 
     R 7  is hydrogen or methyl, 
     and herbicides containing these compounds.

The present invention relates to novel cyclohexanone derivatives having a herbicidal action, to agents based on such cyclohexanone derivatives, and to processes for their preparation and use as herbicides.

The herbicidal action of oxime ethers having a cyclohexenone structure and nonaromatic substituents in the 5-position is known from EP No. 71,707.

It is further known that certain 2-acyl-3-hydroxycyclohex-2-en-1-ones regulate plant growth (EP No. 123,001 and EP No. 126,713).

We have found that cyclohexenone derivatives of the formula ##STR2## where A is oxygen or NOR⁸, where R⁸ is alkyl of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, alkynyl of 3 or 4 carbon atoms, haloalkyl or haloalkenyl of 2 to 4 carbon atoms and 1 to 3 halogen atoms, chlorothienyl or alkoxyalkyl of 2 to 4 carbon atoms,

B is O, S, SO or SO₂,

X is hydrogen or methoxycarbonyl,

R¹ is hydrogen, carbonylalkyl of 2 to 18 carbon atoms or benzoyl or an inorganic or organic cation,

R² is alkyl of up to 4 carbon atoms,

R³ and R⁴, independently of each other, are each hydroxyl, chlorine, bromine, thioalkylcarboxyl, thiocarbonylalkyl, alkylcarbonyloxy each of up to 4 carbon atoms or R³ and R⁴ are together alkoxy of up to 3 carbon atoms and hydroxyl or together alkylthio of up to 3 carbon atoms and hydroxyl or together epoxy,

R⁵ and R⁶, independently of each other, are each hydrogen or methyl or R⁵ and R⁶ are together methyleneoxyethylene,

R⁷ is hydrogen or methyl,

have a powerful herbicidal action, preferably on species of the family of the grasses (Gramineae). They are compatible and thus selective in broad-leaf crops and also in monocotyledons which do not belong to the Gramineae. In addition, numerous compounds are also selective in Gramineae crops such as wheat and rice and at the same time control undesirable grasses. They are biologically superior to comparable compounds.

Examples of R¹ in the formula I are: hydrogen, acetyl, propionyl, butyryl, pivaloyl, palmitoyl, stearoyl, benzoyl, sodium, potassium, ammonium, calcium, magnesium, trialkylammonium, tetraalkylammonium, trialkylbenzylammonium, trialkylsulfonium and trialkylsulfoxonium.

Examples of R² in the formula I are: methyl, ethyl, n-propyl, i-propyl, n-butyl and i-butyl.

Examples of R³ and R⁴ are: alkoxy such as methoxy, ethoxy, n-propoxy or i-propoxy, alkylthio such as methylthio, ethylthio or n-propylthio, hydroxyl, bromine, chlorine, thioalkylcarboxyl such as thiomethylcarboxyl or thioethylcarboxyl, thiocarbonylalkyl such as thiocarbonylmethyl or thiocarbonylethyl, dimethylamino, acetoxy, propionyloxy, butyryloxy and epoxy.

Examples of R⁸ are: methyl, ethyl, n-propyl, i-propyl, allyl, (E)-2-butenyl, 2-fluoroeth-1-yl, 2-chloroeth-1-yl, (E)-3-chloro-2-propenyl, 1,1,2-trichloroprop-1-en-3-yl, chlorothienyl, propargyl, methoxymethyl and methoxyethyl.

The cyclohexenone derivatives of the formula I where A is NOR⁸ and R¹ is hydrogen can be obtained by reacting compounds of the formula ##STR3## where R², R³, R⁴, R⁵, R⁶, R⁷ and X have the abovementioned meanings, with alkoxyammonium compounds of the formula R⁸ ONH₃ Y, where Y is an anion. To this end the two reactants are reacted with each other, for example in a solvent in the presence of a base at from 0° C. to the boiling point of the solvent. Suitable bases are for example carbonates, hydrogencarbonates, acetates, alcoholates, oxides or hydroxides of alkali and alkaline earth metals, in particular sodium, potassium, magnesium or calcium, or organic bases, such as pyridine or tertiary amines.

Suitable solvents are for example dimethyl sulfoxide, alcohols such as methanol, ethanol or isopropanol, benzene, toluene, hydrocarbons and chlorohydrocarbons, such as chloroform, dichloroethane, hexane or cyclohexane, esters, such as ethyl acetate, or ethers, such as dioxane or tetrahydrofuran.

The reaction is complete within a few hours, and the reaction product can be isolated by concentrating the mixture, partitioning the residue between methylene chloride and water and distilling off the solvent under reduced pressure.

The compounds of the formula I where A is NOR⁸ and R¹ is hydrogen can also be obtained by reacting the compounds of the formula I where A is oxygen and R¹ is hydrogen with appropriate alkoxyamines of the formula R⁸ --ONH₂ in a suitable diluent; suitable reaction temperatures range in general from 15° to 70° C. The alkoxyamine can be used in the form of an aqueous solution; depending on the solvent used for the other reactant, a one- or two-phase reaction mixture is obtained.

Suitable solvents for the reaction are for example alcohols, such as methanol, ethanol, isopropanol or cyclohexanol, hydrocarbons and chlorohydrocarbons, such as hexane, cyclohexane, methylene chloride, toluene or dichloroethane, esters, such as ethyl acetate, nitriles, such as acetonitrile, and cyclic ethers, such as tetrahydrofuran.

Alkali metal salts of compounds I can be obtained by treating the compounds with alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium alcoholate or potassium alcoholate in aqueous solution or in an organic solvent, such as methanol, ethanol, acetone or toluene.

Other metal salts, for example the managanese, copper, zinc, iron, calcium, magnesium and barium salts, can be prepared from the sodium salts in a conventional manner (by reaction with salts of the metals with inorganic acids), as in the same way the ammonium and phosphonium salts can be prepared by means of ammonia or phosphonium, sulfonium or sulfoxonium hydroxides.

The compounds of the formula I where A is oxygen can be prepared, for example from the corresponding cyclohexane-1,3-diones II ##STR4## by literature methods (Tetrahedron Lett. 29, (1975), 2491).

It is also possible to prepare compounds of the formula I where A is oxygen via the enol ester intermediate obtained on reacting compounds of the formula II with acid chlorides in the presence of bases and subsequently rearranged with certain imidazole or pyridine derivatives (Japanese Preliminary Published Application No. 79/063,052).

The compounds of the formula II can be obtained by literature methods as given for example in German Laid-Open Application DOS No. 3,219,490.

It is also possible to introduce the substituents R³ and R⁴ at a later stage, preferably directly into compounds of the formula I where A is oxygen.

Suitable precursors are compounds of the formula ##STR5## where literature reactions can be carried out on the double bond, for example addition of halogens, hydrogen halides, mercaptans, thiolcarboxylic acids, mercaptocarboxylic acids or epoxidation.

The epoxy derivatives thus obtained can serve as starting materials for further syntheses based on opening the oxirane ring, for example reaction with mercaptans, water or alcohols with or without acid or base catalysis.

The compounds of the formula I where B is SO or SO₂ can also be obtained by oxidizing appropriate precursors where the sulfur is in a lower state of oxidation. Oxidizing agents are for example oxygen, ozone, peroxy compounds, such as hydrogen peroxides, per-acids, hydroperoxides, halogens, inorganic halogen compounds, such as hypochlorite, chlorate, nitrogen compounds, such as nitric acid and dinitrogen pentoxide, or salts of metals of higher valence, such as lead, bismuth, vanadium, manganese, chromium or cobalt salts. Anodic oxidation is also possible. The oxidation can be carried out not only at the final stage but, in principle, at any stage of the synthesis route described above.

The examples which follow illustrate the preparation of the novel compounds. Parts by weight relate to parts by volume as the kilogram relates to the liter.

EXAMPLE 1

14.8 parts by weight of 2-propionyl-5-(5,6-dihydro-2H-pyran-3-yl)-3-hydroxy-2-cyclohexen-1-one are dissolved in 100 parts by volume of dichloromethane, and m-chloroperbenzoic acid is added at room temperature, and the reaction is monitored by means of thin layer chromatography. After the reaction has ended, the precipitated m-chlorobenzoic acid is filtered off, the filtrate is washed twice with semiconcentrated sodium bicarbonate solution and water and dried over sodium sulfate, and the solvent is distilled off under reduced pressure to leave 2-propionyl-5-(3,4-epoxy-tetrahydropyran-3-yl)-3-hydroxy-2-cyclohexen-1-one (compound No. 30).

EXAMPLE 2

3.0 parts by weight of 2-propionyl-5-(3,4-epoxy-tetrahydropyran-3-yl)-3-hydroxy-2-cyclohex-1-one, 1.8 parts by weight of (E)-3-chloro-2-propenyloxyammonium chloride, 1.1 parts by weight of sodium bicarbonate and 100 parts by volume of methanol are stirred at room temperature for 16 hours. The solvent is distilled off under reduced pressure, 50 parts by volume of water and 50 parts by volume of dichloromethane are added to the residue, after vigorous stirring the phases are separated, and the organic phase is dried over sodium sulfate. Distilling off the solvent under reduced pressure leaves 2-[1-((E)-3-chloro-2-propenyloxyimino)propyl]-5-(3,4-epoxy-tetrahydropyran-3-yl)-3-hydroxy-2-cyclohexen-1-one (compound No. 401).

The following compounds can be obtained in a similar manner:

(The ¹ H-NMR data are given in δ (ppm) and relate to tetramethylsilane as internal standard. Abbreviations: s=singlet, d=dublet, m=multiplet, q=quartet).

                  TABLE 1                                                          ______________________________________                                          ##STR6##                                                                      No.  R.sup.1                                                                               R.sup.2   R.sup.3 and R.sup.4                                                                    B    .sup.1 HNMR data                            ______________________________________                                          1   H      Methyl    Cl      S                                                 2   H      Methyl    Cl      O                                                 3   H      Methyl    Cl      SO                                                4   H      Methyl    Cl      SO.sub.2                                          5   H      Methyl    Br      S                                                 6   H      Methyl    Br      O                                                 7   H      Methyl    Br      SO                                                8   H      Methyl    Br      SO.sub.2                                          9   H      Methyl    OH      S                                                 10  H      Methyl    OH      O                                                 11  H      Methyl    OH      SO                                                12  H      Methyl    OH      SO.sub.2                                          13  H      Methyl    Epoxy   S                                                 14  H      Methyl    Epoxy   O                                                 15  H      Methyl    Epoxy   SO                                                16  H      Methyl    Epoxy   SO.sub.2                                          17  H      Ethyl     Cl      S                                                 18  H      Ethyl     Cl      O                                                 19  H      Ethyl     Cl      SO                                                20  H      Ethyl     Cl      SO.sub.2                                          21  H      Ethyl     Br      S                                                 22  H      Ethyl     Br      O                                                 23  H      Ethyl     Br      SO                                                24  H      Ethyl     Br      SO.sub.2                                          25  H      Ethyl     OH      S                                                 26  H      Ethyl     OH      O                                                 27  H      Ethyl     OH      SO                                                28  H      Ethyl     OH      SO.sub.2                                          29  H      Ethyl     Epoxy   S                                                 30  H      Ethyl     Epoxy   O                                                 31  H      Ethyl     Epoxy   SO                                                32  H      Ethyl     Epoxy   SO.sub.2                                          33  H      n-Propyl  Cl      S                                                 34  H      n-Propyl  Cl      O    1.0(t), 3.9(m), 4.4(m)                       35  H      n-Propyl  Cl      SO                                                36  H      n-Propyl  Cl      SO.sub.2                                          37  H      n-Propyl  Br      S                                                 38  H      n-Propyl  Br      O    2.0(d), 3.0(m), 4.6(s)                       39  H      n-Propyl  Br      SO                                                40  H      n-Propyl  Br      SO.sub.2                                          41  H      n-Propyl  OH      S                                                 42  H      n-Propyl  OH      O    1.0(t), 1.6(q), 3.8(m)                       43  H      n-Propyl  OH      SO                                                44  H      n-Propyl  OH      SO.sub.2                                          45  H      n-Propyl  Epoxy   S                                                 46  H      n-Propyl  Epoxy   O                                                 47  H      n-Propyl  Epoxy   SO                                                48  H      n-Propyl  Epoxy   SO.sub.2                                          49  H      n-Butyl   Cl      S                                                 50  H      n-Butyl   Cl      O                                                 51  H      n-Butyl   Cl      SO                                                52  H      n-Butyl   Cl      SO.sub.2                                          53  H      n-Butyl   Br      S                                                 54  H      n-Butyl   Br      O                                                 55  H      n-Butyl   Br      SO                                                56  H      n-Butyl   Br      SO.sub.2                                          57  H      n-Butyl   OH      S                                                 58  H      n-Butyl   OH      O                                                 59  H      n-Butyl   OH      SO                                                60  H      n-Butyl   OH      SO.sub.2                                          61  H      n-Butyl   Epoxy   S                                                 62  H      n-Butyl   Epoxy   O                                                 63  H      n-Butyl   Epoxy   SO                                                64  H      n-Butyl   Epoxy   SO.sub.2                                          65  Na.sup.+                                                                              Methyl    Cl      S                                                 66  Na.sup.+                                                                              Methyl    Cl      O                                                 67  Na.sup.+                                                                              Methyl    Cl      SO                                                68  Na.sup.+                                                                              Methyl    Cl      SO.sub.2                                          69  Na.sup.+                                                                              Methyl    Br      S                                                 70  Na.sup.+                                                                              Methyl    Br      O                                                 71  Na.sup.+                                                                              Methyl    Br      SO                                                72  Na.sup.+                                                                              Methyl    Br      SO.sub.2                                          73  Na.sup.+                                                                              Methyl    OH      S                                                 74  Na.sup.+                                                                              Methyl    OH      O                                                 75  Na.sup.+                                                                              Methyl    OH      SO                                                76  Na.sup.+                                                                              Methyl    OH      SO.sub.2                                          77  Na.sup.+                                                                              Methyl    Epoxy   S                                                 78  Na.sup.+                                                                              Methyl    Epoxy   O                                                 79  Na.sup.+                                                                              Methyl    Epoxy   SO                                                80  Na.sup.+                                                                              Methyl    Epoxy   SO.sub.2                                          81  Na.sup.+                                                                              Ethyl     Cl      S                                                 82  Na.sup.+                                                                              Ethyl     Cl      O                                                 83  Na.sup.+                                                                              Ethyl     Cl      SO                                                84  Na.sup.+                                                                              Ethyl     Cl      SO.sub.2                                          85  Na.sup.+                                                                              Ethyl     Br      S                                                 86  Na.sup.+                                                                              Ethyl     Br      O                                                 87  Na.sup.+                                                                              Ethyl     Br      SO                                                88  Na.sup.+                                                                              Ethyl     Br      SO.sub.2                                          89  Na.sup.+                                                                              Ethyl     OH      S                                                 90  Na.sup.+                                                                              Ethyl     OH      O                                                 91  Na.sup.+                                                                              Ethyl     OH      SO                                                92  Na.sup.+                                                                              Ethyl     OH      SO.sub.2                                          93  Na.sup.+                                                                              Ethyl     Epoxy   S                                                 94  Na.sup.+                                                                              Ethyl     Epoxy   O                                                 95  Na.sup.+                                                                              Ethyl     Epoxy   SO                                                96  Na.sup.+                                                                              Ethyl     Epoxy   SO.sub.2                                          97  Na.sup.+                                                                              n-Propyl  Cl      S                                                 98  Na.sup.+                                                                              n-Propyl  Cl      O                                                 99  Na.sup.+                                                                              n-Propyl  Cl      SO                                               100  Na.sup.+                                                                              n-Propyl  Cl      SO.sub.2                                         101  Na.sup.+                                                                              n-Propyl  Br      S                                                102  Na.sup.+                                                                              n-Propyl  Br      O                                                103  Na.sup.+                                                                              n-Propyl  Br      SO                                               104  Na.sup.+                                                                              n-Propyl  Br      SO.sub.2                                         105  Na.sup.+                                                                              n-Propyl  OH      S                                                106  Na.sup.+                                                                              n-Propyl  OH      O                                                107  Na.sup.+                                                                              n-Propyl  OH      SO                                               108  Na.sup.+                                                                              n-Propyl  OH      SO.sub.2                                         109  Na.sup.+                                                                              n-Propyl  Epoxy   S                                                110  Na.sup.+                                                                              n-Propyl  Epoxy   O                                                111  Na.sup.+                                                                              n-Propyl  Epoxy   SO                                               112  Na.sup.+                                                                              n-Propyl  Epoxy   SO.sub.2                                         113  Na.sup.+                                                                              n-Butyl   Cl      S                                                114  Na.sup.+                                                                              n-Butyl   Cl      O                                                115  Na.sup.+                                                                              n-Butyl   Cl      SO                                               116  Na.sup.+                                                                              n-Butyl   Cl      SO.sub.2                                         117  Na.sup.+                                                                              n-Butyl   Br      S                                                118  Na.sup.+                                                                              n-Butyl   Br      O                                                119  Na.sup.+                                                                              n-Butyl   Br      SO                                               120  Na.sup.+                                                                              n-Butyl   Br      SO.sub.2                                         121  Na.sup.+                                                                              n-Butyl   OH      S                                                122  Na.sup.+                                                                              n-Butyl   OH      O                                                123  Na.sup.+                                                                              n-Butyl   OH      SO                                               124  Na.sup.+                                                                              n-Butyl   OH      SO.sub.2                                         125  Na.sup.+                                                                              n-Butyl   Epoxy   S                                                126  Na.sup.+                                                                              n-Butyl   Epoxy   O                                                127  Na.sup.+                                                                              n-Butyl   Epoxy   SO                                               128  Na.sup.+                                                                              n-Butyl   Epoxy   SO.sub.2                                         129  K.sup.+                                                                               Methyl    Cl      S                                                130  K.sup.+                                                                               Methyl    Cl      O                                                131  K.sup.+                                                                               Methyl    Cl      SO                                               132  K.sup.+                                                                               Methyl    Cl      SO.sub.2                                         133  K.sup.+                                                                               Methyl    Br      S                                                134  K.sup.+                                                                               Methyl    Br      O                                                135  K.sup.+                                                                               Methyl    Br      SO                                               136  K.sup.+                                                                               Methyl    Br      SO.sub.2                                         137  K.sup.+                                                                               Methyl    OH      S                                                138  K.sup.+                                                                               Methyl    OH      O                                                139  K.sup.+                                                                               Methyl    OH      SO                                               140  K.sup.+                                                                               Methyl    OH      SO.sub.2                                         141  K.sup.+                                                                               Methyl    Epoxy   S                                                142  K.sup.+                                                                               Methyl    Epoxy   O                                                143  K.sup.+                                                                               Methyl    Epoxy   SO                                               144  K.sup.+                                                                               Ethyl     Epoxy   SO.sub.2                                         145  K.sup.+                                                                               Ethyl     Cl      S                                                146  K.sup.+                                                                               Ethyl     Cl      O                                                147  K.sup.+                                                                               Ethyl     Cl      SO                                               148  K.sup.+                                                                               Ethyl     Cl      SO.sub.2                                         149  K.sup.+                                                                               Ethyl     Br      S                                                150  K.sup.+                                                                               Ethyl     Br      O                                                151  K.sup.+                                                                               Ethyl     Br      SO                                               152  K.sup.+                                                                               Ethyl     Br      SO.sub.2                                         153  K.sup.+                                                                               Ethyl     OH      S                                                154  K.sup.+                                                                               Ethyl     OH      O                                                155  K.sup.+                                                                               Ethyl     OH      SO                                               156  K.sup.+                                                                               Ethyl     OH      SO.sub.2                                         157  K.sup.+                                                                               Ethyl     Epoxy   S                                                158  K.sup.+                                                                               Ethyl     Epoxy   O                                                159  K.sup.+                                                                               Ethyl     Epoxy   SO                                               160  K.sup.+                                                                               Ethyl     Epoxy   SO.sub.2                                         161  K.sup.+                                                                               n-Propyl  Cl      S                                                162  K.sup.+                                                                               n-Propyl  Cl      O                                                163  K.sup.+                                                                               n-Propyl  Cl      SO                                               164  K.sup.+                                                                               n-Propyl  Cl      SO.sub.2                                         165  K.sup.+                                                                               n-Propyl  Br      S                                                166  K.sup.+                                                                               n-Propyl  Br      O                                                167  K.sup.+                                                                               n-Propyl  Br      SO                                               168  K.sup.+                                                                               n-Propyl  Br      SO.sub.2                                         169  K.sup.+                                                                               n-Propyl  OH      S                                                170  K.sup.+                                                                               n-Propyl  OH      O                                                171  K.sup.+                                                                               n-Propyl  OH      SO                                               172  K.sup.+                                                                               n-Propyl  OH      SO.sub.2                                         173  K.sup.+                                                                               n-Propyl  Epoxy   S                                                174  K.sup.+                                                                               n-Propyl  Epoxy   O                                                175  K.sup.+                                                                               n-Propyl  Epoxy   SO                                               176  K.sup.+                                                                               n-Propyl  Epoxy   SO.sub.2                                         177  K.sup.+                                                                               n-Butyl   Cl      S                                                178  K.sup.+                                                                               n-Butyl   Cl      O                                                179  K.sup.+                                                                               n-Butyl   Cl      SO                                               180  K.sup.+                                                                               n-Butyl   Cl      SO.sub.2                                         181  K.sup.+                                                                               n-Butyl   Br      S                                                182  K.sup.+                                                                               n-Butyl   Br      O                                                183  K.sup.+                                                                               n-Butyl   Br      SO                                               184  K.sup.+                                                                               n-Butyl   Br      SO.sub.2                                         185  K.sup.+                                                                               n-Butyl   OH      S                                                186  K.sup. +                                                                              n-Butyl   OH      O                                                187  K.sup.+                                                                               n-Butyl   OH      SO                                               188  K.sup.+                                                                               n-Butyl   OH      SO.sub.2                                         189  K.sup.+                                                                               n-Butyl   Epoxy   S                                                190  K.sup.+                                                                               n-Butyl   Epoxy   O                                                191  K.sup.+                                                                               n-Butyl   Epoxy   SO                                               192  K.sup.+                                                                               n-Butyl   Epoxy   SO.sub.2                                         ______________________________________                                    

                                      TABLE 2                                      __________________________________________________________________________      ##STR7##                                                                      No.                                                                               R.sup.1       R.sup.2                                                                             R.sup.3 and R.sup.4                                                                  R.sup.6                                                                            R.sup.7                                                                            B X     .sup.1 HNMR                        __________________________________________________________________________                                                 data                               193                                                                               H             Ethyl                                                                               Epoxy H   H   O COOCH.sub.3                              194                                                                               H             Ethyl                                                                               Cl    H   H   O COOCH.sub.3                              195                                                                               Trimethylbenzylammonium                                                                      n-Propyl                                                                            Epoxy H   H   O H                                        196                                                                               H             n-Propyl                                                                            Epoxy Methyl                                                                             Methyl                                                                             O H                                        197                                                                               H             n-Propyl                                                                            Cl    H   H   O COOCH.sub.3                              198                                                                               H             n-Propyl                                                                            Br    H   H   O COOCH.sub.3                              __________________________________________________________________________

                                      TABLE 3                                      __________________________________________________________________________      ##STR8##                                                                      No.                                                                               R.sup.1       R.sup.2                                                                             R.sup.3 and R.sup.4                                                                  X     .sup.1 HNMR data                             __________________________________________________________________________     199                                                                               H             Methyl                                                                              Cl    H                                                  200                                                                               H             Methyl                                                                              Br    H                                                  201                                                                               H             Methyl                                                                              OH    H                                                  202                                                                               H             Methyl                                                                              Epoxy H                                                  203                                                                               H             Ethyl                                                                               Cl    H                                                  204                                                                               H             Ethyl                                                                               Br    H                                                  205                                                                               H             Ethyl                                                                               OH    H                                                  206                                                                               H             Ethyl                                                                               Epoxy H                                                  207                                                                               H             n-Propyl                                                                            Cl    H                                                  208                                                                               H             n-Propyl                                                                            Br    H     1.0(t), 1.7(q), 4.0(s)                       209                                                                               H             n-Propyl                                                                            OH    H                                                  210                                                                               H             n-Propyl                                                                            Epoxy H     1.0(t), 2.5(m), 4.1(m)                       211                                                                               H             n-Butyl                                                                             Cl    H                                                  212                                                                               H             n-Butyl                                                                             Br    H                                                  213                                                                               H             n-Butyl                                                                             OH    H                                                  214                                                                               H             n-Butyl                                                                             Epoxy H                                                  215                                                                               Na.sup.+      Methyl                                                                              Cl    H                                                  216                                                                               Na.sup.+      Methyl                                                                              Br    H                                                  217                                                                               Na.sup.+      Methyl                                                                              OH    H                                                  218                                                                               Na.sup.+      Methyl                                                                              Epoxy H                                                  219                                                                               Na.sup.+      Ethyl                                                                               Cl    H                                                  220                                                                               Na.sup.+      Ethyl                                                                               Br    H                                                  221                                                                               Na.sup.+      Ethyl                                                                               OH    H                                                  222                                                                               Na.sup.+      Ethyl                                                                               Epoxy H                                                  223                                                                               Na.sup.+      n-Propyl                                                                            Cl    H                                                  224                                                                               Na.sup.+      n-Propyl                                                                            Br    H                                                  225                                                                               Na.sup.+      n-Propyl                                                                            OH    H                                                  226                                                                               Na.sup.+      n-Propyl                                                                            Epoxy H                                                  227                                                                               Na.sup.+      n-Butyl                                                                             Cl    H                                                  228                                                                               Na.sup.+      n-Butyl                                                                             Br    H                                                  229                                                                               Na.sup.+      n-Butyl                                                                             OH    H                                                  230                                                                               Na.sup.+      n-Butyl                                                                             Epoxy H                                                  231                                                                               K.sup.+       Methyl                                                                              Cl    H                                                  232                                                                               K.sup.+       Methyl                                                                              Br    H                                                  233                                                                               K.sup.+       Methyl                                                                              OH    H                                                  234                                                                               K.sup.+       Methyl                                                                              Epoxy H                                                  235                                                                               K.sup.+       Ethyl                                                                               Cl    H                                                  236                                                                               K.sup.+       Ethyl                                                                               Br    H                                                  237                                                                               K.sup.+       Ethyl                                                                               OH    H                                                  238                                                                               K.sup.+       Ethyl                                                                               Epoxy H                                                  239                                                                               K.sup.+       n-Propyl                                                                            Cl    H                                                  240                                                                               K.sup.+       n-Propyl                                                                            Br    H                                                  241                                                                               K.sup.+       n-Propyl                                                                            OH    H                                                  242                                                                               K.sup.+       n-Propyl                                                                            Epoxy H                                                  243                                                                               K.sup.+       n-Butyl                                                                             Cl    H                                                  244                                                                               K.sup.+       n-Butyl                                                                             Br    H                                                  245                                                                               K.sup.+       n-Butyl                                                                             OH    H                                                  246                                                                               K.sup.+       n-Butyl                                                                             Epoxy H                                                  247                                                                               H             n-Propyl                                                                            Cl    COOCH.sub.3                                        248                                                                               H             Ethyl                                                                               Cl    COOCH.sub.3                                        249                                                                               Trimethylbenzylammonium                                                                      Ethyl                                                                               Cl    H                                                  250                                                                               Trimethylbenzylammonium                                                                      n-Propyl                                                                            Cl    H                                                  251                                                                               Tetramethylammonium                                                                          Ethyl                                                                               Epoxy H                                                  252                                                                               Tetramethylammonium                                                                          Ethyl                                                                               Cl    COOCH.sub.3                                        __________________________________________________________________________

                                      TABLE 4                                      __________________________________________________________________________      ##STR9##                                                                      No.                                                                               R.sup.2                                                                             R.sup.3 and R.sup.4                                                                  B  R.sup.5       .sup.1 HNMR data                                __________________________________________________________________________     253                                                                               Methyl                                                                              Cl    S  Ethyl                                                         254                                                                               Methyl                                                                              Cl    S  Allyl                                                         255                                                                               Methyl                                                                              Cl    S  ( .sub.--E)2-Butenyl                                          256                                                                               Methyl                                                                              Cl    S  ( .sub.--E)3-Chloro2-propenyl                                 257                                                                               Methyl                                                                              Cl    S  Propargyl                                                     258                                                                               Methyl                                                                              Cl    O  Ethyl                                                         259                                                                               Methyl                                                                              Cl    O  Allyl                                                         260                                                                               Methyl                                                                              Cl    O  ( .sub.--E)2-Butenyl                                          261                                                                               Methyl                                                                              Cl    O  ( .sub.--E)3-Chloro2-propenyl                                 262                                                                               Methyl                                                                              Cl    O  Propargyl                                                     263                                                                               Methyl                                                                              Cl    SO Ethyl                                                         264                                                                               Methyl                                                                              Cl    SO Allyl                                                         265                                                                               Methyl                                                                              Cl    SO ( .sub.--E)2-Butenyl                                          266                                                                               Methyl                                                                              Cl    SO ( .sub.--E)3-Chloro2-propenyl                                 267                                                                               Methyl                                                                              Cl    SO Propargyl                                                     268                                                                               Methyl                                                                              Cl    SO.sub.2                                                                          Ethyl                                                         269                                                                               Methyl                                                                              Cl    SO.sub.2                                                                          Allyl                                                         270                                                                               Methyl                                                                              Cl    SO.sub.2                                                                          ( .sub.--E)2-Butenyl                                          271                                                                               Methyl                                                                              Cl    SO.sub.2                                                                          ( .sub.--E)3-Chloro2-propenyl                                 272                                                                               Methyl                                                                              Cl    SO.sub.2                                                                          Propargyl                                                     273                                                                               Methyl                                                                              Br    S  Ethyl                                                         274                                                                               Methyl                                                                              Br    S  Allyl                                                         275                                                                               Methyl                                                                              Br    S  ( .sub.--E)2-Butenyl                                          276                                                                               Methyl                                                                              Br    S  ( .sub.--E)3-Chloro2-propenyl                                 277                                                                               Methyl                                                                              Br    S  Propargyl                                                     278                                                                               Methyl                                                                              Br    O  Ethyl                                                         279                                                                               Methyl                                                                              Br    O  Allyl                                                         280                                                                               Methyl                                                                              Br    O  ( .sub.--E)2-Butenyl                                          281                                                                               Methyl                                                                              Br    O  ( .sub.--E)3-Chloro2-propenyl                                 282                                                                               Methyl                                                                              Br    O  Propargyl                                                     283                                                                               Methyl                                                                              Br    SO Ethyl                                                         284                                                                               Methyl                                                                              Br    SO Allyl                                                         285                                                                               Methyl                                                                              Br    SO ( .sub.--E)2-Butenyl                                          286                                                                               Methyl                                                                              Br    SO ( .sub.--E)3-Chloro2-propenyl                                 287                                                                               Methyl                                                                              Br    SO Propargyl                                                     288                                                                               Methyl                                                                              Br    SO.sub.2                                                                          Ethyl                                                         289                                                                               Methyl                                                                              Br    SO.sub.2                                                                          Allyl                                                         290                                                                               Methyl                                                                              Br    SO.sub.2                                                                          ( .sub.--E)2-Butenyl                                          291                                                                               Methyl                                                                              Br    SO.sub.2                                                                          ( .sub.--E)3-Chloro2-propenyl                                 292                                                                               Methyl                                                                              Br    SO.sub.2                                                                          Propargyl                                                     293                                                                               Methyl                                                                              OH    S  Ethyl                                                         294                                                                               Methyl                                                                              OH    S  Allyl                                                         295                                                                               Methyl                                                                              OH    S  ( .sub.--E)2-Butenyl                                          296                                                                               Methyl                                                                              OH    S  ( .sub.--E)3-Chloro2-propenyl                                 297                                                                               Methyl                                                                              OH    S  Propargyl                                                     298                                                                               Methyl                                                                              OH    O  Ethyl                                                         299                                                                               Methyl                                                                              OH    O  Allyl                                                         300                                                                               Methyl                                                                              OH    O  ( .sub.--E)2-Butenyl                                          301                                                                               Methyl                                                                              OH    O  ( .sub.--E)3-Chloro2-propenyl                                 302                                                                               Methyl                                                                              OH    O  Propargyl                                                     303                                                                               Methyl                                                                              OH    SO Ethyl                                                         304                                                                               Methyl                                                                              OH    SO Allyl                                                         305                                                                               Methyl                                                                              OH    S  ( .sub.--E)2-Butenyl                                          306                                                                               Methyl                                                                              OH    SO ( .sub.--E)3-Chloro2-propenyl                                 307                                                                               Methyl                                                                              OH    SO Propargyl                                                     308                                                                               Methyl                                                                              OH    SO.sub.2                                                                          Ethyl                                                         309                                                                               Methyl                                                                              OH    SO.sub.2                                                                          Allyl                                                         310                                                                               Methyl                                                                              OH    SO.sub.2                                                                          ( .sub.--E)2-Butenyl                                          311                                                                               Methyl                                                                              OH    SO.sub.2                                                                          ( .sub.--E)3-Chloro2-propenyl                                 312                                                                               Methyl                                                                              OH    SO.sub.2                                                                          Propargyl                                                     313                                                                               Methyl                                                                              Epoxy S  Ethyl                                                         314                                                                               Methyl                                                                              Epoxy S  Allyl                                                         315                                                                               Methyl                                                                              Epoxy S  ( .sub.--E)2-Butenyl                                          316                                                                               Methyl                                                                              Epoxy S  ( .sub.--E)3-Chloro2-propenyl                                 317                                                                               Methyl                                                                              Epoxy S  Propargyl                                                     318                                                                               Methyl                                                                              Epoxy O  Ethyl                                                         319                                                                               Methyl                                                                              Epoxy O  Allyl                                                         320                                                                               Methyl                                                                              Epoxy O  (  .sub.--E)2-Butenyl                                         321                                                                               Methyl                                                                              Epoxy O  ( .sub.--E)3-Chloro2-propenyl                                 322                                                                               Methyl                                                                              Epoxy O  Propargyl                                                     323                                                                               Methyl                                                                              Epoxy SO Ethyl                                                         324                                                                               Methyl                                                                              Epoxy SO Allyl                                                         325                                                                               Methyl                                                                              Epoxy SO ( .sub.--E)2-Butenyl                                          326                                                                               Methyl                                                                              Epoxy SO ( .sub.--E)3-Chloro2-propenyl                                 327                                                                               Methyl                                                                              Epoxy O  Propargyl                                                     328                                                                               Methyl                                                                              Epoxy SO.sub.2                                                                          Ethyl                                                         329                                                                               Methyl                                                                              Epoxy SO.sub.2                                                                          Allyl                                                         330                                                                               Methyl                                                                              Epoxy SO.sub.2                                                                          ( .sub.--E)2-Butenyl                                          331                                                                               Methyl                                                                              Epoxy SO.sub.2                                                                          ( .sub.--E)3-Chloro2-propenyl                                 332                                                                               Methyl                                                                              Epoxy SO.sub.2                                                                          Propargyl                                                     333                                                                               Ethyl                                                                               Cl    S  Ethyl                                                         334                                                                               Ethyl                                                                               Cl    S  Allyl                                                         335                                                                               Ethyl                                                                               Cl    S  ( .sub.--E)2-Butenyl                                          336                                                                               Ethyl                                                                               Cl    S  ( .sub.--E)3-Chloro2-propenyl                                 337                                                                               Ethyl                                                                               Cl    S  Propargyl                                                     338                                                                               Ethyl                                                                               Cl    S  Ethyl                                                         339                                                                               Ethyl                                                                               Cl    O  Allyl                                                         340                                                                               Ethyl                                                                               Cl    O  ( .sub.--E)2-Butenyl                                          341                                                                               Ethyl                                                                               Cl    O  ( .sub.--E)3-Chloro2-propenyl                                 342                                                                               Ethyl                                                                               Cl    O  Propargyl                                                     343                                                                               Ethyl                                                                               Cl    SO Ethyl                                                         344                                                                               Ethyl                                                                               Cl    SO Allyl                                                         345                                                                               Ethyl                                                                               Cl    SO ( .sub.--E) 2-Butenyl                                         346                                                                               Ethyl                                                                               Cl    SO ( .sub.--E)3-Chloro2-propenyl                                 347                                                                               Ethyl                                                                               Cl    O  Propargyl                                                     348                                                                               Ethyl                                                                               Cl    SO.sub.2                                                                          Ethyl                                                         349                                                                               Ethyl                                                                               Cl    SO.sub.2                                                                          Allyl                                                         350                                                                               Ethyl                                                                               Cl    SO.sub.2                                                                          ( .sub.--E)2-Butenyl                                          351                                                                               Ethyl                                                                               Cl    SO.sub.2                                                                          ( .sub.--E)3-Chloro2-propenyl                                 352                                                                               Ethyl                                                                               Cl    SO.sub.2                                                                          Propargyl                                                     353                                                                               Ethyl                                                                               Br    S  Ethyl                                                         354                                                                               Ethyl                                                                               Br    S  Allyl                                                         355                                                                               Ethyl                                                                               Br    S  ( .sub.--E)2-Butenyl                                          356                                                                               Ethyl                                                                               Br    S  ( .sub.--E)3-Chloro2-propenyl                                 357                                                                               Ethyl                                                                               Br    S  Propargyl                                                     358                                                                               Ethyl                                                                               Br    O  Ethyl                                                         359                                                                               Ethyl                                                                               Br    O  Allyl                                                         360                                                                               Ethyl                                                                               Br    O  ( .sub.--E)2-Butenyl                                          361                                                                               Ethyl                                                                               Br    O  ( .sub.--E)3-Chloro2-propenyl                                 362                                                                               Ethyl                                                                               Br    O  Propargyl                                                     363                                                                               Ethyl                                                                               Br    SO Ethyl                                                         364                                                                               Ethyl                                                                               Br    SO Allyl                                                         365                                                                               Ethyl                                                                               Br    SO ( .sub.--E)2-Butenyl                                          366                                                                               Ethyl                                                                               Br    SO ( .sub.--E)3-Chloro2-propenyl                                 367                                                                               Ethyl                                                                               Br    SO Propargyl                                                     368                                                                               Ethyl                                                                               Br    SO.sub.2                                                                          Ethyl                                                         369                                                                               Ethyl                                                                               Br    SO.sub.2                                                                          Allyl                                                         370                                                                               Ethyl                                                                               Br    SO.sub.2                                                                          ( .sub.--E)2-Butenyl                                          371                                                                               Ethyl                                                                               Br    SO.sub.2                                                                          ( .sub.--E)3-Chloro2-propenyl                                 372                                                                               Ethyl                                                                               Br    SO.sub.2                                                                          Propargyl                                                     373                                                                               Ethyl                                                                               OH    S  Ethyl                                                         374                                                                               Ethyl                                                                               OH    S  Allyl                                                         375                                                                               Ethyl                                                                               OH    S  ( .sub.--E)2-Butenyl                                          376                                                                               Ethyl                                                                               OH    S  ( .sub.--E)3-Chloro2-propenyl                                 377                                                                               Ethyl                                                                               OH    S  Propargyl                                                     378                                                                               Ethyl                                                                               OH    O  Ethyl                                                         379                                                                               Ethyl                                                                               OH    O  Allyl                                                         380                                                                               Ethyl                                                                               OH    O  ( .sub.--E)2-Butenyl                                          381                                                                               Ethyl                                                                               OH    O  ( .sub.--E)3-Chloro2-propenyl                                 382                                                                               Ethyl                                                                               OH    O  Propargyl                                                     383                                                                               Ethyl                                                                               OH    SO Ethyl                                                         384                                                                               Ethyl                                                                               OH    SO Allyl                                                         385                                                                               Ethyl                                                                               OH    SO ( .sub.--E)2-Butenyl                                          386                                                                               Ethyl                                                                               OH    SO ( .sub.--E)3-Chloro2-propenyl                                 387                                                                               Ethyl                                                                               OH    SO Propargyl                                                     388                                                                               Ethyl                                                                               OH    SO.sub.2                                                                          Ethyl                                                         389                                                                               Ethyl                                                                               OH    SO.sub.2                                                                          Allyl                                                         390                                                                               Ethyl                                                                               OH    SO.sub.2                                                                          ( .sub.--E)2-Butenyl                                          391                                                                               Ethyl                                                                               OH    SO.sub.2                                                                          ( .sub.--E)3-Chloro2-propenyl                                 392                                                                               Ethyl                                                                               OH    SO.sub.2                                                                          Propargyl                                                     393                                                                               Ethyl                                                                               Epoxy S  Ethyl                                                         394                                                                               Ethyl                                                                               Epoxy S  Allyl                                                         395                                                                               Ethyl                                                                               Epoxy S  ( .sub.--E)2-Butenyl                                          396                                                                               Ethyl                                                                               Epoxy S  ( .sub.--E)3-Chloro2-propenyl                                 397                                                                               Ethyl                                                                               Epoxy S  Propargyl                                                     398                                                                               Ethyl                                                                               Epoxy O  Ethyl         1.3(t), 2.5(m), 3.3(s)                          399                                                                               Ethyl                                                                               Epoxy O  Allyl         1.3(t), 3.5(m), 4.6(d)                          400                                                                               Ethyl                                                                               Epoxy O  ( .sub.--E)2-Butenyl                                          401                                                                               Ethyl                                                                               Epoxy O  ( .sub.--E)3-Chloro2-propenyl                                                                2.0(m), 3.5(m), 6.35(d)                         402                                                                               Ethyl                                                                               Epoxy O  Propargyl                                                     403                                                                               Ethyl                                                                               Epoxy SO Ethyl                                                         404                                                                               Ethyl                                                                               Epoxy SO Allyl                                                         405                                                                               Ethyl                                                                               Epoxy SO ( .sub.--E)2-Butenyl                                          406                                                                               Ethyl                                                                               Epoxy SO ( .sub.--E)3-Chloro2-propenyl                                 407                                                                               Ethyl                                                                               Epoxy SO Propargyl                                                     408                                                                               Ethyl                                                                               Epoxy SO.sub.2                                                                          Ethyl                                                         409                                                                               Ethyl                                                                               Epoxy SO.sub.2                                                                          Allyl                                                         410                                                                               Ethyl                                                                               Epoxy SO.sub.2                                                                          ( .sub.--E)2-Butenyl                                          411                                                                               Ethyl                                                                               Epoxy SO.sub.2                                                                          ( .sub.--E)3-Chloro2-propenyl                                 412                                                                               Ethyl                                                                               Epoxy SO.sub.2                                                                          Propargyl                                                     413                                                                               n-Propyl                                                                            Cl    S  Ethyl                                                         414                                                                               n-Propyl                                                                            Cl    S  Allyl                                                         415                                                                               n-Propyl                                                                            Cl    S  ( .sub.--E)2-Butenyl                                          416                                                                               n-Propyl                                                                            Cl    S  ( .sub.--E)3-Chloro2-propenyl                                 417                                                                               n-Propyl                                                                            Cl    S  Propargyl                                                     418                                                                               n-Propyl                                                                            Cl    O  Ethyl         1.3(t), 1.6(q), 4.4(s)                          419                                                                               n-Propyl                                                                            Cl    O  Allyl                                                         420                                                                               n-Propyl                                                                            Cl    O  ( .sub.-- E)2-Butenyl                                         421                                                                               n-Propyl                                                                            Cl    O  ( .sub.--E)3-Chloro2-propenyl                                                                1.0(t), 3.9(m), 4.5(d)                          422                                                                               n-Propyl                                                                            Cl    O  Propargyl                                                     423                                                                               n-Propyl                                                                            Cl    SO Ethyl                                                         424                                                                               n-Propyl                                                                            Cl    SO Allyl                                                         425                                                                               n-Propyl                                                                            Cl    SO ( .sub.--E)2-Butenyl                                          426                                                                               n-Propyl                                                                            Cl    SO ( .sub.--E)3-Chloro2-propenyl                                 427                                                                               n-Propyl                                                                            Cl    SO Propargyl                                                     428                                                                               n-Propyl                                                                            Cl    SO.sub.2                                                                          Ethyl                                                         429                                                                               n-Propyl                                                                            Cl    SO.sub.2                                                                          Allyl                                                         430                                                                               n-Propyl                                                                            Cl    SO.sub.2                                                                          ( .sub.--E)2-Butenyl                                          431                                                                               n-Propyl                                                                            Cl    SO.sub.2                                                                          ( .sub.--E)3-Chloro2-propenyl                                 432                                                                               n-Propyl                                                                            Cl    SO.sub.2                                                                          Propargyl                                                     433                                                                               n-Propyl                                                                            Br    S  Ethyl                                                         434                                                                               n-Propyl                                                                            Br    S  Allyl                                                         435                                                                               n-Propyl                                                                            Br    S  ( .sub.--E)2-Butenyl                                          436                                                                               n-Propyl                                                                            Br    S  ( .sub.--E)3-Chloro2-propenyl                                 437                                                                               n-Propyl                                                                            Br    S  Propargyl                                                     438                                                                               n-Propyl                                                                            Br    O  Ethyl         1.3(t), 3.9(m), 4.65(s)                         439                                                                               n-Propyl                                                                            Br    O  Allyl         1.9(d), 4.5(d), 4.6(s)                          440                                                                               n-Propyl                                                                            Br    O  ( .sub.--E)2-Butenyl                                                                         0.95(t), 1.8(d), 4.6(s)                         441                                                                               n-Propyl                                                                            Br    O  ( .sub.--E)3-Chloro2-propenyl                                                                0.95(t), 1.5(q), 6.3(d)                         442                                                                               n-Propyl                                                                            Br    O  Propargyl                                                     443                                                                               n-Propyl                                                                            Br    SO Ethyl                                                         444                                                                               n-Propyl                                                                            Br    SO Allyl                                                         445                                                                               n-Propyl                                                                            Br    SO ( .sub.--E)2-Butenyl                                          446                                                                               n-Propyl                                                                            Br    SO ( .sub.--E)3-Chloro2-propenyl                                 447                                                                               n-Propyl                                                                            Br    SO Propargyl                                                     448                                                                               n-Propyl                                                                            Br    SO.sub.2                                                                          Ethyl                                                         449                                                                               n-Propyl                                                                            Br    SO.sub.2                                                                          Allyl                                                         450                                                                               n-Propyl                                                                            Br    SO.sub.2                                                                          ( .sub.--E)2-Butenyl                                          451                                                                               n-Propyl                                                                            Br    SO.sub.2                                                                          ( .sub.--E)3-Chloro2-propenyl                                 452                                                                               n-Propyl                                                                            Br    SO.sub.2                                                                          Propargyl                                                     453                                                                               n-Propyl                                                                            OH    S  Ethyl                                                         454                                                                               n-Propyl                                                                            OH    S  Allyl                                                         455                                                                               n-Propyl                                                                            OH    S  ( .sub.--E)2-Butenyl                                          456                                                                               n-Propyl                                                                            OH    S  ( .sub.--E)3-Chloro2-propenyl                                 457                                                                               n-Propyl                                                                            OH    S  Propargyl                                                     458                                                                               n-Propyl                                                                            OH    O  Ethyl         1.0(t), 2.6(m), 4.1(q)                          459                                                                               n-Propyl                                                                            OH    O  Allyl                                                         460                                                                               n-Propyl                                                                            OH    O  ( .sub.--E)2-Butenyl                                          461                                                                               n-Propyl                                                                            OH    O  ( .sub.--E)3-Chloro2-propenyl                                 462                                                                               n-Propyl                                                                            OH    O  Propargyl                                                     463                                                                               n-Propyl                                                                            OH    SO Ethyl                                                         464                                                                               n-Propyl                                                                            OH    SO Allyl                                                         465                                                                               n-Propyl                                                                            OH    SO ( .sub.--E)2-Butenyl                                          466                                                                               n-Propyl                                                                            OH    SO ( .sub.--E)3-Chloro2-propenyl                                 467                                                                               n-Propyl                                                                            OH    SO Propargyl                                                     468                                                                               n-Propyl                                                                            OH    SO.sub.2                                                                          Ethyl                                                         469                                                                               n-Propyl                                                                            OH    SO.sub.2                                                                          Allyl                                                         470                                                                               n-Propyl                                                                            OH    SO.sub.2                                                                          ( .sub.--E)2-Butenyl                                          471                                                                               n-Propyl                                                                            OH    SO.sub.2                                                                          ( .sub.--E)3-Chloro2-propenyl                                 472                                                                               n-Propyl                                                                            OH    SO.sub.2                                                                          Propargyl                                                     473                                                                               n-Propyl                                                                            Epoxy S  Ethyl                                                         474                                                                               n-Propyl                                                                            Epoxy S  Allyl                                                         475                                                                               n-Propyl                                                                            Epoxy S  ( .sub.--E)2-Butenyl                                          476                                                                               n-Propyl                                                                            Epoxy S  ( .sub.--E)3-Chloro2-propenyl                                 477                                                                               n-Propyl                                                                            Epoxy S  Propargyl                                                     478                                                                               n-Propyl                                                                            Epoxy O  Ethyl         1.35(t), 2.0(m), 3.3(s)                         479                                                                               n-Propyl                                                                            Epoxy O  Allyl                                                         480                                                                               n-Propyl                                                                            Epoxy O  ( .sub.--E)2-Butenyl                                                                         0.95(t), 1.5(m), 3.3(s)                         481                                                                               n-Propyl                                                                            Epoxy O  ( .sub.--E)3-Chloro2-propenyl                                 482                                                                               n-Propyl                                                                            Epoxy O  Propargyl                                                     483                                                                               n-Propyl                                                                            Epoxy SO Ethyl                                                         484                                                                               n-Propyl                                                                            Epoxy SO Allyl                                                         485                                                                               n-Propyl                                                                            Epoxy SO ( .sub.--E)2-Butenyl                                          486                                                                               n-Propyl                                                                            Epoxy SO ( .sub.--E)3-Chloro2-propenyl                                 487                                                                               n-Propyl                                                                            Epoxy SO Propargyl                                                     488                                                                               n-Propyl                                                                            Epoxy SO.sub.2                                                                          Ethyl                                                         489                                                                               n-Propyl                                                                            Epoxy SO.sub.2                                                                          Allyl                                                         490                                                                               n-Propyl                                                                            Epoxy SO.sub.2                                                                          ( .sub.--E)2-Butenyl                                          491                                                                               n-Propyl                                                                            Epoxy SO.sub.2                                                                          ( .sub.-- E)3-Chloro2-propenyl                                492                                                                               n-Propyl                                                                            Epoxy SO.sub.2                                                                          Propargyl                                                     493                                                                               n-Butyl                                                                             Cl    S  Ethyl                                                         494                                                                               n-Butyl                                                                             Cl    S  Allyl                                                         495                                                                               n-Butyl                                                                             Cl    S  ( .sub.--E)2-Butenyl                                          496                                                                               n-Butyl                                                                             Cl    S  ( .sub.--E)3-Chloro2-propenyl                                 497                                                                               n-Butyl                                                                             Cl    S  Propargyl                                                     498                                                                               n-Butyl                                                                             Cl    O  Ethyl                                                         499                                                                               n-Butyl                                                                             Cl    O  Allyl                                                         500                                                                               n-Butyl                                                                             Cl    O  ( .sub.--E)2-Butenyl                                          501                                                                               n-Butyl                                                                             Cl    O  ( .sub.--E)3-Chloro2-propenyl                                 502                                                                               n-Butyl                                                                             Cl    O  Propargyl                                                     503                                                                               n-Butyl                                                                             Cl    SO Ethyl                                                         504                                                                               n-Butyl                                                                             Cl    SO Allyl                                                         505                                                                               n-Butyl                                                                             Cl    SO ( .sub.--E)2-Butenyl                                          506                                                                               n-Butyl                                                                             Cl    SO ( .sub.--E)3-Chloro2-propenyl                                 507                                                                               n-Butyl                                                                             Cl    SO Propargyl                                                     508                                                                               n-Butyl                                                                             Cl    SO.sub.2                                                                          Ethyl                                                         509                                                                               n-Butyl                                                                             Cl    SO.sub.2                                                                          Allyl                                                         510                                                                               n-Butyl                                                                             Cl    SO.sub.2                                                                          ( .sub.--E)2-Butenyl                                          511                                                                               n-Butyl                                                                             Cl    SO.sub.2                                                                          ( .sub.--E)3-Chloro2-propenyl                                 512                                                                               n-Butyl                                                                             Cl    SO.sub.2                                                                          Propargyl                                                     513                                                                               n-Butyl                                                                             Br    S  Ethyl                                                         514                                                                               n-Butyl                                                                             Br    S  Allyl                                                         515                                                                               n-Butyl                                                                             Br    S  ( .sub.--E)2-Butenyl                                          516                                                                               n-Butyl                                                                             Br    S  ( .sub.--E)3-Chloro2-propenyl                                 517                                                                               n-Butyl                                                                             Br    S  Propargyl                                                     518                                                                               n-Butyl                                                                             Br    O  Ethyl                                                         519                                                                               n-Butyl                                                                             Br    O  Allyl                                                         520                                                                               n-Butyl                                                                             Br    O  ( .sub.--E)2-Butenyl                                          521                                                                               n-Butyl                                                                             Br    O  ( .sub.--E)3-Chloro2-propenyl                                 522                                                                               n-Butyl                                                                             Br    O  Propargyl                                                     523                                                                               n-Butyl                                                                             Br    SO Ethyl                                                         524                                                                               n-Butyl                                                                             Br    SO Allyl                                                         525                                                                               n-Butyl                                                                             Br    SO ( .sub.--E)2-Butenyl                                          526                                                                               n-Butyl                                                                             Br    SO ( .sub.--E)3-Chloro2-propenyl                                 527                                                                               n-Butyl                                                                             Br    SO Propargyl                                                     528                                                                               n-Butyl                                                                             Br    SO.sub.2                                                                          Ethyl                                                         529                                                                               n-Butyl                                                                             Br    SO.sub.2                                                                          Allyl                                                         530                                                                               n-Butyl                                                                             Br    SO.sub.2                                                                          ( .sub.--E)2-Butenyl                                          531                                                                               n-Butyl                                                                             Br    SO.sub.2                                                                          ( .sub.--E)3-Chloro2-propenyl                                 532                                                                               n-Butyl                                                                             Br    SO.sub.2                                                                          Propargyl                                                     533                                                                               n-Butyl                                                                             OH    S  Ethyl                                                         534                                                                               n-Butyl                                                                             OH    S  Allyl                                                         535                                                                               n-Butyl                                                                             OH    S  ( .sub.--E)2-Butenyl                                          536                                                                               n-Butyl                                                                             OH    S  ( .sub.--E)3-Chloro2-propenyl                                 537                                                                               n-Butyl                                                                             OH    S  Propargyl                                                     538                                                                               n-Butyl                                                                             OH    O  Ethyl                                                         539                                                                               n-Butyl                                                                             OH    O  Allyl                                                         540                                                                               n-Butyl                                                                             OH    O  ( .sub.--E)2-Butenyl                                          541                                                                               n-Butyl                                                                             OH    O  ( .sub.--E)3-Chloro2-propenyl                                 542                                                                               n-Butyl                                                                             OH    O  Propargyl                                                     543                                                                               n-Butyl                                                                             OH    SO Ethyl                                                         544                                                                               n-Butyl                                                                             OH    SO Allyl                                                         545                                                                               n-Butyl                                                                             OH    SO ( .sub.--E)2-Butenyl                                          546                                                                               n-Butyl                                                                             OH    SO ( .sub.--E)3-Chloro2-propenyl                                 547                                                                               n-Butyl                                                                             OH    SO Propargyl                                                     548                                                                               n-Butyl                                                                             OH    SO.sub.2                                                                          Ethyl                                                         549                                                                               n-Butyl                                                                             OH    SO.sub.2                                                                          Allyl                                                         550                                                                               n-Butyl                                                                             OH    SO.sub.2                                                                          ( .sub.--E)2-Butenyl                                          551                                                                               n-Butyl                                                                             OH    SO.sub.2                                                                          ( .sub.--E)3-Chloro2-propenyl                                 552                                                                               n-Butyl                                                                             OH    SO.sub.2                                                                          Propargyl                                                     553                                                                               n-Butyl                                                                             Epoxy S  Ethyl                                                         554                                                                               n-Butyl                                                                             Epoxy S  Allyl                                                         555                                                                               n-Butyl                                                                             Epoxy S  ( .sub.--E)2-Butenyl                                          556                                                                               n-Butyl                                                                             Epoxy S  ( .sub.--E)3-Chloro2-propenyl                                 557                                                                               n-Butyl                                                                             Epoxy S  Propargyl                                                     558                                                                               n-Butyl                                                                             Epoxy O  Ethyl                                                         559                                                                               n-Butyl                                                                             Epoxy O  Allyl                                                         560                                                                               n-Butyl                                                                             Epoxy O  ( .sub.--E)2-Butenyl                                          561                                                                               n-Butyl                                                                             Epoxy O  ( .sub.--E)3-Chloro2-propenyl                                 562                                                                               n-Butyl                                                                             Epoxy O  Propargyl                                                     563                                                                               n-Butyl                                                                             Epoxy SO Ethyl                                                         564                                                                               n-Butyl                                                                             Epoxy SO Allyl                                                         565                                                                               n-Butyl                                                                             Epoxy SO ( .sub.--E)2-Butenyl                                          566                                                                               n-Butyl                                                                             Epoxy SO ( .sub.--E)3-Chloro2-propenyl                                 567                                                                               n-Butyl                                                                             Epoxy SO Propargyl                                                     568                                                                               n-Butyl                                                                             Epoxy SO.sub.2                                                                          Ethyl                                                         569                                                                               n-Butyl                                                                             Epoxy SO.sub.2                                                                          Allyl                                                         570                                                                               n-Butyl                                                                             Epoxy SO.sub.2                                                                          ( .sub.--E)2-Butenyl                                          571                                                                               n-Butyl                                                                             Epoxy SO.sub.2                                                                          ( .sub.--E)3-Chloro2-propenyl                                 572                                                                               n-Butyl                                                                             Epoxy SO.sub.2                                                                          Propargyl                                                     __________________________________________________________________________

                                      TABLE 5                                      __________________________________________________________________________      ##STR10##                                                                     No.                                                                               R.sup.1                                                                             R.sup.2                                                                             R.sup.3                                                                              R.sup.4   R.sup.6 and R.sup.7                                                                  R.sup.8                                                                              .sup.1 HNMR data                      __________________________________________________________________________     573                                                                               H    n-Propyl                                                                            OH    Dimethylamino                                                                            H     Ethyl                                       574                                                                               H    n-Propyl                                                                            OH    Methylthio                                                                               H     Ethyl                                       575                                                                               H    n-Propyl                                                                            OH    Ethylthio H     Ethyl                                       576                                                                               H    n-Propyl                                                                            OH    Thiocarbonylmethyl                                                                       H     Ethyl                                       577                                                                               H    n-Propal                                                                            OH    Thiomethylcarboxyl                                                                       H     Ethyl                                       578                                                                               H    n-Propyl                                                                            H     Methylthio                                                                               H     Ethyl                                       579                                                                               H    n-Propyl                                                                            H     Ethylthio H     Ethyl                                       580                                                                               H    n-Propyl                                                                            H     Thiocarbonylmethyl                                                                       H     Ethyl                                       581                                                                               H    n-Propyl                                                                            H     Thiomethylcarbonyl                                                                       H     Ethyl                                       582                                                                               Benzoyl                                                                             n-Propyl                                                                            OH    Methylthio                                                                               H     Ethyl                                       583                                                                               H    Ethyl                                                                               H     Thiocarbonylmethyl                                                                       H     Ethyl                                       584                                                                               H    Ethyl                                                                               H     Thiocarbonylmethyl                                                                       H     Allyl                                       585                                                                               H    Ethyl                                                                               H     Thiocarbonylmethyl                                                                       H     Propargyl                                   586                                                                               H    Methyl                                                                              H     Thiocarbonylmethyl                                                                       H     Ethyl                                       587                                                                               H    Methyl                                                                              H     Thiocarbonylmethyl                                                                       H     Allyl                                       588                                                                                Benzoyl                                                                            n-Propyl                                                                            R.sup.3 and R.sup.4 = Epoxy                                                                    H     Ethyl                                       589                                                                               Stearoyl                                                                            n-Propyl                                                                            R.sup.3 and R.sup.4 = Epoxy                                                                    H     Ethyl                                       590                                                                               H    n-Propyl                                                                            Methylthio                                                                           OH        Methyl                                                                               Ethyl                                       591                                                                               H    n-Propyl                                                                            Ethylthio                                                                            OH        Methyl                                                                               Ethyl                                       672                                                                               H    n-Propyl                                                                            R.sup.3 and R.sup.4 = Epoxy                                                                    Methyl                                                                               Ethyl 0.96(t), 3.91(q),                     __________________________________________________________________________                                              4.09(q)                          

                  TABLE 6                                                          ______________________________________                                          ##STR11##                                                                                   R.sup.3 and           .sup.1 HNMR                                No.  R.sup.2  R.sup.4 R.sup.8       data                                       ______________________________________                                         592  Methyl   Cl      Ethyl                                                    593  Methyl   Cl      Allyl                                                    594  Methyl   Cl      ( .sub.--E)-2-Butenyl                                    595  Methyl   Cl      ( .sub.--E)-3-Chloro-2-propenyl                          596  Methyl   Cl      Propargyl                                                597  Methyl   Br      Ethyl                                                    598  Methyl   Br      Allyl                                                    599  Methyl   Br      ( .sub.--E)-2-Butenyl                                    600  Methyl   Br      ( .sub.--E)-3-Chloro-2-propenyl                          601  Methyl   Br      Propargyl                                                602  Methyl   OH      Ethyl                                                    603  Methyl   OH      Allyl                                                    604  Methyl   OH      ( .sub.--E)-2-Butenyl                                    605  Methyl   OH      ( .sub.--E)-3-Chloro-2-propenyl                          606  Methyl   OH      Propargyl                                                607  Methyl   Epoxy   Ethyl                                                    608  Methyl   Epoxy   Allyl                                                    609  Methyl   Epoxy   ( .sub.--E)-2-Butenyl                                    610  Methyl   Epoxy   ( .sub.--E)-3-Chloro-2-propenyl                          611  Methyl   Epoxy   Propargyl                                                612  Ethyl    Cl      Ethyl                                                    613  Ethyl    Cl      Allyl                                                    614  Ethyl    Cl      ( .sub.--E)-2-Butenyl                                    615  Ethyl    Cl      ( .sub.--E)-3-Chloro-2-propenyl                          616  Ethyl    Cl      Propargyl                                                617  Ethyl    Br      Ethyl                                                    618  Ethyl    Br      Allyl                                                    619  Ethyl    Br      ( .sub.--E)-2-Butenyl                                    620  Ethyl    Br      ( .sub.--E)-3-Chloro-2-propenyl                          621  Ethyl    Br      Propargyl                                                622  Ethyl    OH      Ethyl                                                    623  Ethyl    OH      Allyl                                                    624  Ethyl    OH      ( .sub.--E)-2-Butenyl                                    625  Ethyl    OH      ( .sub.--E)-3-Chloro-2-propenyl                          626  Ethyl    OH      Propargyl                                                627  Ethyl    Epoxy   Ethyl                                                    628  Ethyl    Epoxy   Allyl                                                    629  Ethyl    Epoxy   ( .sub.--E)-2-Butenyl                                    630  Ethyl    Epoxy   ( .sub.--E)-3-Chloro-2-propenyl                          631  Ethyl    Epoxy   Propargyl                                                632  n-Propyl Cl      Ethyl                                                    633  n-Propyl Cl      Allyl                                                    634  n-Propyl Cl      ( .sub.--E)-2-Butenyl                                    635  n-Propyl Cl      ( .sub.--E)-3-Chloro-2-propenyl                          636  n-Propyl Cl      Propargyl                                                637  n-Propyl Br      Ethyl         1.6(q), 2.6(m),                                                                4.1(q)                                     638  n-Propyl Br      Allyl         1.0(t), 3.9(m),                                                                5.4(m)                                     639  n-Propyl Br      ( .sub.--E)-2-Butenyl                                                                        1.0(t), 1.7(d),                                                                2.9(m)                                     640  n-Propyl Br      ( .sub.--E)-3-Chloro-2-propenyl                                                              1.5(q), 2.9(t),                                                                4.0(s)                                     641  n-Propyl Br      Propargyl                                                642  n-Propyl OH      Ethyl                                                    643  n-Propyl OH      Allyl                                                    644  n-Propyl OH      ( .sub.--E)-2-Butenyl                                    645  n-Propyl OH      ( .sub.--E)-3-Chloro-2-propenyl                          646  n-Propyl OH      Propargyl                                                647  n-Propyl Epoxy   Ethyl         1.3(t), 2.3(m),                                                                3.1(s)                                     648  n-Propyl Epoxy   Allyl         0.95(t), 3.1(s),                                                               4.5(d)                                     649  n-Propyl Epoxy   ( .sub.--E)-2-Butenyl                                    650  n-Propyl Epoxy   ( .sub.--E)-3-Chloro-2-propenyl                                                              1.35(t),                                                                       2.0(m), 3.3(s)                             651  n-Propyl Epoxy   Propargyl                                                652  n-Butyl  Cl      Ethyl                                                    653  n-Butyl  Cl      Allyl                                                    654  n-Butyl  Cl      ( .sub.--E)-2-Butenyl                                    655  n-Butyl  Cl      ( .sub.--E)-3-Chloro-2-propenyl                          656  n-Butyl  Cl      Propargyl                                                657  n-Butyl  Br      Ethyl                                                    658  n-Butyl  Br      Allyl                                                    659  n-Butyl  Br      ( .sub.--E)-2-Butenyl                                    660  n-Butyl  Br      ( .sub.--E)-3-Chloro-2-propenyl                          661  n-Butyl  Br      Propargyl                                                662  n-Butyl  OH      Ethyl                                                    663  n-Butyl  OH      Allyl                                                    664  n-Butyl  OH      ( .sub.--E)-2-Butenyl                                    665  n-Butyl  OH      ( .sub.--E)-3-Chloro-2-propenyl                          666  n-Butyl  OH      Propargyl                                                667  n-Butyl  Epoxy   Ethyl                                                    668  n-Butyl  Epoxy   Allyl                                                    669  n-Butyl  Epoxy   ( .sub.--E)-2-Butenyl                                    670  n-Butyl  Epoxy   ( .sub.--E)-3-Chloro-2-propenyl                          671  n-Butyl  Epoxy   Propargyl                                                ______________________________________                                    

                                      TABLE 7                                      __________________________________________________________________________     No.                                                                               A   B X R.sup.1                                                                             R.sup.2                                                                            R.sup.3                                                                          R.sup.4                                                                          R.sup.5                                                                             R.sup.6                                                                            R.sup.7                                                                          R.sup.8                                     __________________________________________________________________________     673                                                                               NOR.sup.8                                                                          O H C.sub.3 H.sub.7 CO                                                                  Propyl                                                                             O   CH.sub.2 OC.sub.2 H.sub.4                                                               H Ethyl                                                                              0.90(t), 1.0(t), 1.24(t)                674                                                                               NOR.sup.8                                                                          O H Benzoyl                                                                             Propyl                                                                             O   CH.sub.2 OC.sub.2 H.sub.4                                                               H Ethyl                                                                              0.86(t), 1.09(t), 7.3-8.2(m)            675                                                                               NOR.sup.8                                                                          O H Acetyl                                                                              Propyl                                                                             O   CH.sub.2 OC.sub.2 H.sub.4                                                               H Ethyl                                                                              0.88(t), 1.25(t),                       __________________________________________________________________________                                            2.19(s)                            

The cyclohexenone derivatives of the formula I, and their salts, may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.

For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, and paraffin, tetrahydrocarbons such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol or formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate and ureas, and vegetable products such as grain flours, bark meal, wood meal and nutshell meal, cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably from 0.5 to 90, % by weight of active ingredient.

Examples of formulations are given below.

I. 90 parts by weight of compound no. 647 is mixed with 10 parts by weight of N-methyl-α-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

II. 20 parts by weight of compound no. 648 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of active ingredient.

III. 20 parts by weight of compound no. 650 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of active ingredient.

IV. 20 parts by weight of compound no. 637 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210° and 280° C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of active ingredient.

V. 20 parts by weight of compound no. 638 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of a ligninsulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1% by weight of active ingredient.

VI. 3 parts by weight of compound no. 640 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of active ingredient.

VII. 30 parts by weight of compound no. 478 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

VIII. 20 parts of compound no. 480 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

IX. 10 parts by weight of compound no. 440 is mixed with 90 parts by weight of a mixture consisting of 93 parts by weight of xylene and 7 parts by weight of the adduct of 8 moles of ethylene oxide and 1 mole of nonylphenol. A solution is obtained containing 10 wt% of the active ingredient.

The active ingredients, or agents containing them, may be applied pre- or postemergence. If certain crop plants tolerate the active ingredients less well, application techniques may be used in which the herbicidal agents are sprayed from suitable equipment in such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post-directed, lay-by treatment).

The amounts of active ingredient applied depends on the time of the year, the plants to be combated and their growth stage, and varies from 0.01 to 3 kg/ha, but is preferably from 0.05 to 0.5 kg/ha.

The action of the cyclohexenone derivatives of the formula I on plant growth is demonstrated in greenhouse experiments.

The vessels employed were plastic flowerpots having a volume of 300 cm³, and which were filled with a sandy loam containing about 3.0% humus. The seeds of the test plants were sown shallow, and separately, according to species. For the preemergence treatment, the active ingredients were applied to the surface of the soil immediately after the seeds had been sown. The compounds were emulsified or suspended in water as vehicle, and sprayed through finely distributing nozzles. The application rate was 3.0 kg of active ingredient per hectare. After the agents had been applied, the vessels were lightly sprinkler-irrigated to induce germination and growth. Transparent plastic covers were then placed on the vessels until the plants had taken root. The cover ensured uniform germination of the plants, insofar as this was not impaired by the active ingredients.

For the postemergence treatment, the plants were first grown in the vessels to a height of from 3 to 15 cm, depending on growth form, before being treated. For this treatment, either plants which had been sown directly in the pots and grown there were selected, or plants which had been grown from seedlings and were transplanted to the pots a few days before treatment. The application rate for postemergence treatment was 0.125 kg of active ingredient per hectare. No covers were placed on the vessels in this method.

The pots were set up in the greenhouse--species from warmer areas at from 20° C. to 35° C., and species from moderate climates at 10° to 25° C. The experiments were run for 2 to 4 weeks. During this period, the plants were tended and their reactions to the various treatments assessed. The scale used for assessment was 0 to 100, 0 denoting no damage or normal emergence, and 100 denoting nonemergence or complete destruction of at least the visible plant parts.

The plants used in the experiments were Alopecurus myosuroides, Avena fatua, Avena sativa, Digitaria sanguinalis, Echinochloa crus-galli, Lolium multiflorum, Medicago sativa, Setaria italica, Sinapis alba, Sorghum halepense, Triticum aestivum, and Zea mays.

Grasses from the Gramineae family were well combated with a preemergence application of 3.0 kg/ha of, for example, compounds 647, 648, 650, 637, 638, 640, 478, 480 and 440. Sinapis alba (broadleaved crop plant) suffered no damage whatsoever.

Compounds 647, 648, 650 and 401 are suitable, at a rate of 0.125 kg/ha, for controlling, postemergence, a broad spectrum of unwanted grassy plants. Volunteer crop plants from the Gramineae family are also combated. Alfalfa--a broadleaved crop plant--remain completely uninfluenced.

Unwanted grassy species are well combated by postemergence applications of active ingredients 438, 439 and 674; wheat remains unaffected.

In view of the spectrum of weeds which can be combated, the tolerance of the active ingredients according to the invention by crop plants, the desired influence on the growth of crop plants, and in view of the numerous application methods possible, the compounds according to the invention may be used in a large number of crop plants.

The following crops may be mentioned by way of example:

    ______________________________________                                         Botanical name       Common name                                               ______________________________________                                         Allium cepa          onions                                                    Ananas comosus       pineapples                                                Arachis hypogaea     peanuts (groundnuts)                                      Asparagus officinalis                                                                               asparagus                                                 Beta vulgaris spp. altissima                                                                        sugarbeets                                                Beta vulgaris spp. rapa                                                                             fodder beets                                              Beta vulgaris spp. esculenta                                                                        table beets, red beets                                    Brassica napus var. napus                                                                           rapeseed                                                  Brassica napus var. napobrassica                                                                    swedes                                                    Brassica napus var. rapa                                                                            turnips                                                   Brassica rapa var. silvestris                                                  Camellia sinensis    tea plants                                                Carthamus tinctorius safflower                                                 Carya illinoinensis  pecan trees                                               Citrus limon         lemons                                                    Citrus maxima        grapefruits                                               Citrus reticulata    mandarins                                                 Citrus sinensis      orange trees                                              Coffea arabica (Coffea canephora,                                                                   coffee plants                                             Coffea liberica)                                                               Cucumis melo         melons                                                    Cucumis sativus      cucumbers                                                 Cynodon dactylon     bermudagrass                                              Daucus carota        carrots                                                   Elaeis guineensis    oil palms                                                 Fragaria vesca       strawberries                                              Glycine max          soybeans                                                  Gossypium hirsutum (Gossypium                                                                       cotton                                                    arboreum, Gossypium herbaceum,                                                 Gossypium vitifolium)                                                          Helianthus annuus    sunflowers                                                Helianthus tuberosus Jerusalem artichoke                                       Hevea brasiliensis   rubber plants                                             Hordeum vulgare      barley                                                    Humulus lupulus      hops                                                      Ipomoea batatas      sweet potatoes                                            Juglans regia        walnut trees                                              Lactua sativa        lettuce                                                   Lens culinaris       lentils                                                   Linum usitatissimum  flax                                                      Lycopersicon lycopersicum                                                                           tomatoes                                                  Malus spp.           apple trees                                               Manihot esculenta    cassava                                                   Medicago sativa      alfalfa (lucerne)                                         Mentha piperita      peppermint                                                Musa spp.            banana plants                                             Nicotiana tabacum (N. rustica)                                                                      tobacco                                                   Olea europaea        olive trees                                               Oryza sativa         rice                                                      Phaseolus lunatus    limabeans                                                 Phaseolus mungo      mungbeans                                                 Phaseolus vulgaris   snapbeans,                                                                     green beans, dry beans                                    Pennisetum glaucum   pearl millet                                              Petroselinum crispum spp. tuberosum                                                                 parsley                                                   Picea abies          Norway spruce                                             Abies alba           fir trees                                                 Pinus spp.           pine trees                                                Pisum sativum        English peas                                              Prunus avium         cherry trees                                              Prunus domestica     plum trees                                                Prunus dulcis        almond trees                                              Prunus persica       peach trees                                               Pyrus communis       pear trees                                                Ribes sylvestre      redcurrants                                               Ribes uva-crispa     gooseberries                                              Ricinus communis     castor-oil plants                                         Saccharum officinarum                                                                               sugar cane                                                Secale cereale       rye                                                       Sesamum indicum      sesame                                                    Solanum tuberosum    Irish potatoes                                            Spinacia oleracea    spinach                                                   Theobroma cacao      cacao plants                                              Trifolium pratense   red clover                                                Triticum aestivum    wheat                                                     Vaccinium corymbosum blueberries                                               Vaccinium vitis-idaea                                                                               cranberries                                               Vicia faba           tick beans                                                Vigna sinensis (V. unguiculata)                                                                     cow peas                                                  Vitis vinifera       grapes                                                    Zea mays             Indian corn,                                                                   sweet corn, maize                                         ______________________________________                                    

To increase the spectrum of action and to achieve synergistic effects, the cyclohexenone derivatives of the formula I may be mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples or suitable mixture components are diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, quinolinecarboxylic acid derivatives, etc.

It may also be useful to apply the compounds of the formula I, or herbicidal agents containing them, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or phytopathogenic fungi or bacteria. The compounds may also be mixed with solutions of mineral salts used to remedy nutritional or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added. 

We claim:
 1. A cyclohexenone derivative of the formula ##STR12## where A is oxygen or NOR⁸, where R⁸ is alkyl of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, alkynyl of 3 or 4 carbon atoms, haloalkyl or haloalkenyl of 2 to 4 carbon atoms and 1 to 3 halogen atoms, chlorothienyl or alkoxyalkyl of 2 to 4 carbon atoms,B is 0, X is hydrogen or methoxycarbonyl, R¹ is hydrogen, carbonylalkyl of 2 to 18 carbon atoms or benzoyl or an inorganic or organic cation, R² is alkyl of up to 4 carbon atoms, R³ and R⁴, independently of each other, are each hydroxyl, chlorine, bromine, thioalkylcarboxyl, thiocarbonylalkyl, alkylcarbonyloxy each of up to 4 carbon atoms or R³ and R⁴ are together alkoxy of up to 3 carbon atoms and hydroxyl or together alkylthio of up to 3 carbon atoms and hydroxyl or together form an epoxy group, R⁵ and R⁶, independently of each other, are each hydrogen or methyl or R⁵ and R⁶ together form a methyleneoxyethylene group, and R⁷ is hydrogen or methyl.
 2. A cyclohexenone derivative as set forth in claim 1, where A is NOR⁸, B is oxygen, X is hydrogen, R¹ is hydrogen, R² is ethyl or propyl, each of R³ and R⁴ is bromine or R³ and R⁴ together are an epoxy group, each of R⁵ and R⁶ is hydrogen or R⁵ and R⁶ together are a methyleneoxyethylene group, R⁷ is hydrogen, and R⁸ is ethyl, allyl, chloropropenyl or butenyl.
 3. The cyclohexenone derivative of the formula I as defined in claim 1 which is2-(1-((E)-2-butenyloxyimino)butyl)-5-(1,6-dibromo-tetrahydropyran-3-yl)-3-hydroxy-2-cyclohexen-1-one.
 4. A herbicide containing an inert additive and an effective amount of a compound of the formula ##STR13## where A is oxygen or NOR⁸, where R⁸ is alkyl of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, alkynyl of 3 or 4 carbon atoms, haloalkyl or haloalkenyl of 2 to 4 carbon atoms and 1 to 3 halogen atoms, chlorothienyl or alkoxyalkyl of 2 to 4 carbon atoms,B is 0, X is hydrogen or methoxycarbonyl, R¹ is hydrogen, carbonylalkyl of 2 to 18 carbon atoms or benzoyl or an inorganic or organic cation, R² is alkyl of up to 4 carbon atoms, R³ and R⁴, independently of each other, are each hydroxyl, chlorine, bromine, thioalkylcarboxyl, thiocarbonylalkyl, alkylcarbonyloxy each of up to 4 carbon atoms or R³ and R⁴ are together alkoxy of up to 3 carbon atoms and hydroxyl or together alkylthio of up to 3 carbon atoms and hydroxyl or together form an epoxy group, R⁵ and R⁶, independently of each other, are each hydrogen or methyl or R⁵ and R⁶ together form a methyleneoxyethylene group, and R⁷ is hydrogen or methyl.
 5. A herbicide as set forth in claim 4 containing an effective amount of a compound of the formula I, where A is NOR⁸, B is oxygen, X is hydrogen, R¹ is hydrogen, R² is ethyl or propyl, each of R³ and R⁴ is bromine or R³ and R⁴ together are an epoxy group, R⁵ and R⁶ are each hydrogen or R⁵ and R⁶ together are a methyleneoxyethylene group, R⁷ is hydrogen, and R⁸ is ethyl, allyl, chloropropenyl or butenyl.
 6. A process for combating the growth of unwanted plants, wherein the unwanted plants or the area to be kept free from unwanted plant growth are treated with a herbicidally effective amount of a compound of the formula ##STR14## where A is oxygen or NOR⁸, where R⁸ is alkyl of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, alkynyl of 3 or 4 carbon atoms, haloalkyl or haloalkenyl of 2 to 4 carbon atoms and 1 to 3 halogen atoms, chlorothienyl or alkoxyalkyl of 2 to 4 carbon atoms,B is 0, X is hydrogen or methoxycarbonyl, R¹ is hydrogen, carbonylalkyl of 2 to 18 carbon atoms or benzoyl or an inorganic or organic cation, R² is alkyl of up to 4 carbon atoms, R³ and R⁴, independently of each other, are each hydroxyl, chlorine, bromine, thioalkylcarboxyl, thiocarbonylalkyl, alkylcarbonyloxy each of up to 4 carbon atoms or R³ and R⁴ are together alkoxy of up to 3 carbon atoms and hydroxyl or together alkylthio of up to 3 carbon atoms and hydroxyl or together form an epoxy group, R⁵ and R⁶, independently of each other, are each hydrogen or methyl or R⁵ and R⁶ together form a methyleneoxyethylene group, and R⁷ is hydrogen or methyl. 